Copper‐Catalyzed Enantioselective Domino Arylation/Semipinacol Rearrangement of Allylic Alcohols with Diaryliodonium Salts

A copper‐catalyzed enantioselective arylative semipinacol rearrangement of allylic alcohols was developed. In the presence of a catalytic amount of an in situ generated chiral copper‐bisoxazoline complex, reaction of allylic alcohols with diaryliodonium salts afforded spirocycloalkanones in high yields with high diastereo‐ and enantioselectivities. A two‐point binding model engaging the carbon–carbon double bond and the proximal hydroxyl group was proposed to be responsible for the highly efficient chirality transfer.